U.S. patent number 9,548,150 [Application Number 13/786,807] was granted by the patent office on 2017-01-17 for cerium-iron-based magnetic compounds.
This patent grant is currently assigned to GM Global Technology Operations LLC. The grantee listed for this patent is GM GLOBAL TECHNOLOGY OPERATIONS LLC. Invention is credited to Jan F. Herbst, Frederick E. Pinkerton, Chen Zhou.
United States Patent |
9,548,150 |
Zhou , et al. |
January 17, 2017 |
Cerium-iron-based magnetic compounds
Abstract
New magnetic materials containing cerium, iron, and small
additions of a third element are disclosed. These materials
comprise compounds Ce(Fe.sub.12-xM.sub.x) where x=1-4, having the
ThMn.sub.12 tetragonal crystal structure (space group I4/mmm,
#139). Compounds with M=B, Al, Si, P, S, Sc, Co, Ni, Zn, Ga, Ge,
Zr, Nb, Hf, Ta, and W are identified theoretically, and one class
of compounds based on M=Si has been synthesized. The Si cognates
are characterized by large magnetic moments (4.pi.M.sub.s greater
than 1.27 Tesla) and high Curie temperatures
(264.ltoreq.T.sub.c.ltoreq.305.degree. C.). The
Ce(Fe.sub.12-xM.sub.x) compound may contain one or more of Ti, V,
Cr, and Mo in combination with an M element. Further enhancement in
T.sub.c is obtained by nitriding the Ce compounds through heat
treatment in N.sub.2 gas while retaining the ThMn.sub.12 tetragonal
crystal structure; for example CeFe.sub.10Si.sub.2N.sub.1.29 has
T.sub.c=426.degree. C.
Inventors: |
Zhou; Chen (Warren, MI),
Pinkerton; Frederick E. (Shelby Township, MI), Herbst; Jan
F. (Grosse Pointe Woods, MI) |
Applicant: |
Name |
City |
State |
Country |
Type |
GM GLOBAL TECHNOLOGY OPERATIONS LLC |
Detroit |
MI |
US |
|
|
Assignee: |
GM Global Technology Operations
LLC (Detroit, MI)
|
Family
ID: |
51486354 |
Appl.
No.: |
13/786,807 |
Filed: |
March 6, 2013 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20140251500 A1 |
Sep 11, 2014 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01F
1/0593 (20130101) |
Current International
Class: |
H01F
1/057 (20060101); H01F 1/055 (20060101); H01F
1/059 (20060101); H01F 1/058 (20060101) |
Field of
Search: |
;148/221,230,301,302,306,307,310,311,300,315,317,331
;420/416,128,83,121,117 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
V Lachevre, B. Barbara, D. Fruchart, L. Pontonnier A new type of
soft ferromagnetic alloys: RFe12--xGex Journal of Alloys and
Compounds vol. 275-277, 24, Jul. 1998, pp. 615-619. cited by
examiner .
Y. Y Z. Wang and G. C. Hadjipanayis Effect of nitrogen on the
structural and magnetic properties of intermetallic compounds with
the ThMn12 structure Journal of Applied Physics vol. 70, No. 10 15,
Nov. 1991. cited by examiner .
Shunji Suzuki, Naomi noue, and Toshihiko Miura Mangetic Properties
of RFe11--xCoxTiNy (R: Nd, Pr) compounds with ThMn12 Type structure
IEEE Transations on magnetic, vol. 28, No. 5, Sep. 1992. cited by
examiner .
K. G. Efthimiadis, S.C. Chadjivasiliou, A.K. Sianou, I.A.
Tsoukalas, G. Kitsardakis, H. Bremers, J. Hesse Structural
investigations of NdFe12--x--yTixNby alloys Journal of Magnetism
and Magnetic Materials 242-245 (2002) 1381-1383. cited by examiner
.
K. Ohashi, Y. Tawara, R. Osugi, and M. Shimao Magnetic properties
of Fe-rich rare-earth intermetallic compounds with a ThMn12
structure J. Appl. Phys. 64 (10), Nov. 15, 1988 pp. 5714-5716.
cited by examiner .
S. Obbadea , b ,*, D. Fruchartb, M. Bououdinab, S. Miragliab, J.L.
Soubeyrouxb, O. Isnardb About hydrogen insertion in ThMn12 type
alloys Journal of Alloys and Compounds 253-254 (1997) 298-301.
cited by examiner.
|
Primary Examiner: Roe; Jessee
Assistant Examiner: Wu; Jenny
Attorney, Agent or Firm: Reising Ethington P.C.
Government Interests
This invention was made with U.S. Government support under
Agreement No. DE-AR0000195 awarded by the Department of Energy. The
U.S. Government may have certain rights in this invention.
Claims
The invention claimed is:
1. A permanent magnet material containing the compound,
Ce(Fe.sub.12-xSi.sub.x), having the tetragonal ThMn.sub.12 crystal
structure, space group I4/mmm, #139 and where x has a value in the
range of one to four, the compound Ce(Fe.sub.12-xSi.sub.x), having
been prepared from a melt consisting of cerium, iron, and silicon
and the melt having been rapidly solidified at a cooling rate to
form particles of a permanent magnet material containing the
compound having the tetragonal ThMn.sub.12 crystal structure, space
group I4/mmm, #139, the particles of permanent magnet material
having a magnetic moment value, 4.pi.Ms, in the range of 1.04 to
1.27 Tesla, the Ce(Fe.sub.12-xSi.sub.x) compound contains one or
more of Ti, V, Cr, and Mo in combination with Si such that the
combination provides a value of x in the range of 1-4 and Si
comprises at least 0.1 x.
2. A permanent magnet material as stated in claim 1 and containing
at least seventy percent by weight of the Ce(Fe.sub.12-xSi.sub.x)
compound.
3. A permanent magnet material containing the compound,
Ce(Fe.sub.12-xSi.sub.x), having the tetragonal ThMn.sub.12 crystal
structure, space group I4/mmm, #139 and where x has a value in the
range of one to four, the compound Ce(Fe.sub.12-xSi.sub.x), having
been prepared from a melt consisting of cerium, iron, and silicon
and the melt having been rapidly solidified at a cooling rate to
form particles of a permanent magnet material containing the
compound having the tetragonal ThMn.sub.12 crystal structure, space
group I4/mmm, #139, the particles of permanent magnet material
having a magnetic moment value, 4.pi.Ms, in the range of 1.04 to
1.27 Tesla, the Ce(Fe.sub.12-xSi.sub.x) compound containing
nitrogen, Ce(Fe.sub.12-xSi.sub.x)N.sub.y, the value of y being from
one to three such that the nitrogen is present in an amount up to
three nitrogen atoms per formula unit for increasing the Curie
temperature, T.sub.c, of the material as compared with the T.sub.c
of the same Ce(Fe.sub.12-xSi.sub.x) compound without the
nitrogen.
4. A permanent magnet material as stated in claim 3 and containing
at least seventy percent by weight of the crystalline
Ce(Fe.sub.12-xSi.sub.x)N.sub.y compound.
5. A permanent magnet material as stated in claim 1 in which the
Ce(Fe.sub.12-xSi.sub.x) compound further containing nitrogen in an
amount up to three nitrogen atoms per formula unit, the nitrogen
being present in an amount for increasing the Curie temperature,
T.sub.c, of the material as compared with the T.sub.c of the same
Ce(Fe.sub.12-xSi.sub.x) compound without the nitrogen.
6. A permanent magnet material as stated in claim 2 in the form of
a consolidated particle permanent magnet.
7. A permanent magnet material as stated in claim 4 in the form of
a consolidated particle permanent magnet.
8. A permanent magnet material as stated in claim 5 in the form of
a consolidated particle permanent magnet.
Description
TECHNICAL FIELD
This invention provides new magnetic materials containing cerium,
iron, and small additions of a third element(s), and comprising
compounds Ce(Fe.sub.12-xM.sub.x) having the ThMn.sub.12 tetragonal
crystal structure (space group I4/mmm, #139). Compounds with M=B,
Al, Si, P, S, Sc, Ti, V, Co, Ni, Zn, Ga, Ge, Zr, Nb, Mo, Hf, Ta,
and W are identified theoretically, and one class of compounds
based on M=Si has been synthesized. The Si cognates are
characterized by large magnetic moments 4.pi.M.sub.s (above 1.27
Tesla) and high Curie temperatures
(264.ltoreq.T.sub.c.ltoreq.305.degree. C.). Further enhancement in
T.sub.c and magnetic moment is obtained by nitriding the cerium
compounds through heat treatment in nitrogen gas while retaining
the ThMn.sub.12 crystal structure; for example
CeFe.sub.10Si.sub.2N.sub.1.29 has T.sub.c==426.degree. C.
BACKGROUND OF THE INVENTION
There remains a need for permanent magnet materials in electric
motors for many applications and in other magnet-containing
articles of manufacture. Cerium-iron compounds are attractive
candidates to explore as potential permanent magnet materials.
However, they have a low Curie temperature which will impede their
use in major automotive applications (e.g., traction motors)
because they will not retain sufficient magnetic properties in a
device at elevated operating temperatures. It appears that if
cerium-iron materials are to be thus utilized their compositions
will have to be modified.
SUMMARY OF THE INVENTION
This invention provides a new series of Ce--Fe-based permanent
magnet materials based on the presence in the material of a major
portion of one or more compounds of the form
Ce(Fe.sub.12-xM.sub.x), where M is one or more elements selected
from the group consisting of B, Al, Si, P, S, Sc, Co, Ni, Zn, Ga,
Ge, Zr, Nb, Hf, Ta, and W. The material is prepared with the
Ce(Fe.sub.12-xM.sub.x) compound(s) in the form of a stable
ThMn.sub.12 tetragonal crystal structure (sometimes referred to as
1-12) to provide the permanent magnet properties. Preferably the
value of x is in the range of 1-4. Compounds containing an M
element from the above listing may additionally include one or more
of Ti, V, Cr, and/or Mo along with one or more of the
M-constituents. In general, it is preferred that the Ce--Fe-M
magnetic materials be prepared by a suitable process, such as by
rapid solidification from a melt of the constituent elements, to
achieve the presence of a major phase of Ce(Fe.sub.12-xM.sub.x) in
the ThMn.sub.12 tetragonal crystal structure and with x in the
range of 1-4.
The above listed elements, M, forming a stable ThMn.sub.12-type
crystal structure with cerium and iron are identified in this
specification using first-principles theoretical calculations based
on Density Functional Theory (DFT) using the representative
compound, CeFe.sub.8M.sub.4. In addition to the DFT calculations,
examples of stable ThMn.sub.12-type compounds have been synthesized
with M=Si having stoichiometries CeFe.sub.12-xSi.sub.x (x=1, 1.5,
and 2).
Permanent magnet alloys containing CeFe.sub.11Si,
CeFe.sub.10.5Si.sub.1.5, and CeFe.sub.10Si.sub.2 were prepared by
combining stoichiometric quantities of elemental Ce, Fe, and Si in
an ingot. Ingots of these materials were then melted under inert
gas and subjected to a rapid solidification process to form ribbon
particles. The ribbon particles were comminuted to a powder and
magnetically characterized. The magnetic moment (saturation
magnetization) 4.pi.M.sub.s may be approximated by the value of the
magnetization 4.pi.M at the largest applied magnetic field (H) of
1.9 Tesla; given that the magnetization is still slowly increasing
with H at 1.9 Tesla, the values of 4.pi.M.sub.s presented in this
application thus represent lower limits to the actual saturation
magnetization. The three CeFe.sub.12-xSi.sub.x alloys were found to
have large magnetic moments 4.pi.M.sub.s=1.04 to 1.27 Tesla and
Curie temperatures, 264.degree. C.<T.sub.c<305.degree. C.,
which are higher than the Curie temperatures of any previously
known Ce--Fe-based compounds. Curie temperatures are further
improved by heat treatment under nitrogen gas to form the
corresponding CeFe.sub.12-xM.sub.xN.sub.y nitrides, while retaining
the ThMn.sub.12 crystal structure. The nitride
CeFe.sub.10Si.sub.2N.sub.1.29 boasts a Curie temperature of
426.degree. C. and a higher magnetic moment than its precursor,
CeFe.sub.10Si.sub.2.
Accordingly, we have prepared specific CeFe.sub.12-xSi.sub.x
compositions where x=1, 1.5, and 2, and demonstrated that they
possess useful permanent magnetic properties. And we have
determined that a family of compositionally related compounds is
likely to be formable in a like manner into useful permanent magnet
materials. These related compounds are Ce(Fe.sub.12-xM.sub.x),
where M is one or more elements selected from the group consisting
of B, Al, Si, P, S, Sc, Co, Ni, Zn, Ga, Ge, Zr, Nb, Hf, Ta, or W.
In these compounds it is preferred that x have a value in the range
of one to four. Proportions of one or more of Ti, V, Cr, and Mo may
be combined with or substituted for up to about ninety percent of
one of the M elements in our Ce--Fe-M magnetic material; for
example, CeFe.sub.10.25Si.sub.1.5Ti.sub.0.25.
The magnetic material may be prepared in powder form for
compacting, molding, resin bonding, or other shaping practice into
a useful permanent magnet body for use in an electric motor or
other magnet application. Other objects and advantages of our
invention will be apparent from the following sections of this
specification.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a Rietveld analysis fit of an X-ray diffraction
pattern on a sample of CeFe.sub.10Si.sub.2 melt spun at 15 m/s
based on the three most probable phases: the hypothetical
ThMn.sub.12-type CeFe.sub.10Si.sub.2 crystal phase, the
Fe.sub.0.95Si.sub.0.05 phase, and the Ce.sub.2Fe.sub.14Si.sub.3
phase. The unfitted three minor peaks at 34.9, 38.7, and 46.8
degrees 2.THETA. belong to SiO.sub.2. The short vertical lines (|)
of row (a) mark the Bragg positions for CeFe.sub.10Si.sub.2, row
(b) for Fe.sub.0.95Si.sub.0.05, and row (c) for
Ce.sub.2Fe.sub.14Si.sub.3.
FIG. 2 is a graph of phase concentration (wt %) for
CeFe.sub.12-xSi.sub.x (x=1, 1.5, 2) alloys melt spun at 5 m/s, 15
m/s, and 30 m/s, respectively. The designation 1-12 in the legend
represents the ThMn.sub.12 crystal structure, Fe represents Fe--Si
compound, and 2-17 refers to Ce.sub.2Fe.sub.17-ySi.sub.y.
FIG. 3 is a graph of lattice constants in Angstrom units (.ANG.) as
a function of silicon (Si) content in CeFe.sub.12-xSi.sub.x for
x=1, 1.5, and 2. The values of lattice constants in .ANG. on the
left-side vertical axis are for a (filled diamonds) and the lattice
constants in .ANG. on the right vertical axis are for c (filled
squares).
FIG. 4 is a graph of crystallite size in nanometers (nm) as a
function of melt-spin wheel speed in m/s for selected
CeFe.sub.12-xSi.sub.x alloys.
FIG. 5 (a) presents a graph of lattice expansion versus nitriding
time in hours and FIG. 5(b) presents a graph of volume expansion
versus nitriding time in hours after nitriding of a sample of
CeFe.sub.12Si.sub.2 melt spun at v.sub.S=15 m/s. In FIG. 5(a)
values of the lattice constant a in Angstroms (filled diamonds) are
presented on the left-side vertical axis and values of the lattice
constant c (filled squares) are presented on the right vertical
axis. Data at 0 hour nitriding time represent values for
un-nitrided base alloy. In FIG. 5(b), lattice volumes in cubic
Angstroms are presented on the left vertical axis and volume
expansions in (%) are presented on the right vertical axis.
FIG. 6 is an X-ray diffraction pattern of melt spun
CeFe.sub.10+xSi.sub.2-2xTi.sub.x, where x=0, 0.25, 0.5, 0.75, and
1. The as-spun samples typically consist of primary
ThMn.sub.12-type phase with minor Fe-based impurity phase (denoted
as .alpha.-Fe in the figure).
FIG. 7 is a graph of lattice constants of melt spun
CeFe.sub.10+xSi.sub.2-2xTi.sub.x, where x=0, 0.25, 0.5, 0.75, and
1. The values of the lattice constants a in .ANG. (filled diamonds)
are on the left vertical axis and the values of the lattice
constants c in .ANG. (filled squares) are on the right vertical
axis.
FIG. 8 is a graph of Curie temperatures T.sub.c of the base ternary
and quaternary compounds (filled diamonds) of
CeFe.sub.10+xSi.sub.2-2xTi.sub.x (where x=0, 0.25, 0.5, 0.75, and
1), and their respective nitrides (filled triangles).
DESCRIPTION OF PREFERRED EMBODIMENTS
First principles Density Functional Theory (DFT) was applied in
order to computationally identify elements M for which
CeFe.sub.12-xM.sub.x compounds having the prototypical tetragonal
ThMn.sub.12-type crystal structure may form. In that structure the
Th ions occupy 2a crystallographic sites; the Mn ions reside on 8i,
8j, and 8f sites. Neutron diffraction studies of known
RFe.sub.12-xM.sub.x materials (R=rare earth) demonstrate that the M
ions show distinct site preferences among the 8i, 8j, and 8f sites.
Within the preferred crystallographic site, however, the Fe and M
ions are disordered. Treating the intra-site disorder on such high
occupancy sites is a daunting computational challenge. Instead,
elements M that might stabilize the ThMn.sub.12 structure are
qualitatively identified via a much more tractable approach:
element M is assumed to fully occupy the 8i, 8j, or 8f sites in the
ThMn.sub.12 structure, corresponding to the stoichiometry,
CeFe.sub.8M.sub.4, and the enthalpy of formation, .DELTA.H, is
computed for each of the three cases. A negative .DELTA.H suggests
the formation of CeFe.sub.12-xM.sub.x.
All calculations reported here rely on DFT as implemented in the
Vienna ab initio simulation package (VASP) within a plane wave
basis set. Potentials constructed by the projector-augmented wave
(PAW) method were employed for the elements; the generalized
gradient approximation was used for the exchange-correlation energy
functional. As a consequence of 4f shell instability, the cerium
ion in intermetallic compounds is often in a mixed-valent,
.alpha.-like state that is incompatible with a local 4f magnetic
moment. In view of the fact that only 3+ (one 4f electron in a
frozen core) and 4+ (one 4f electron treated variationally with two
5s, six 5p, and three 5d-6s electrons) PAW potentials are available
in VASP, the latter was chosen as the preferable approximation for
the materials studied. Lattice constants and atomic positions were
optimized by simultaneously minimizing all atomic forces and stress
tensor components via a conjugate gradient method. Dense reciprocal
space meshes having spacings <0.10 .ANG..sup.-1 were used
throughout. In all computations the plane wave cutoff energy was
900 eV, the total energy was converged to 10.sup.-6 eV per cell,
and the force components relaxed to at least 10.sup.-4 eV/.ANG.. No
fewer than three successive full-cell optimizations were conducted
to ensure that the structural parameters and cell energies were
fully converged. Total energies were derived by integration over
the irreducible Brillouin zone with the linear tetrahedron
method.
The electronic total energies E.sub.el obtained with VASP enable
calculation of .DELTA.H.sub.el(CeFe.sub.8M.sub.4), the standard
enthalpy of CeFe.sub.8M.sub.4 formation at zero temperature in the
absence of zero point energy contributions:
.DELTA.H.sub.el(CeFe.sub.8M.sub.4).ident.E.sub.el(CeFe.sub.8M.sub.4)-E.su-
b.el(Ce)-8E.sub.el(Fe)-4E.sub.el(M) (1).
In the case of the progenitor compound CeFe.sub.12 this yields
.DELTA.H.sub.el(CeFe.sub.12)=E.sub.el(CeFe.sub.12)-E.sub.el(Ce)-12E.sub.e-
l(Fe)=11 kJ/mole CeFe.sub.12 (2); the positive value is consistent
with the experimental observation that CeFe.sub.12 does not form
under normal conditions.
Table I presents .DELTA.H.sub.el, the magnetic moment .mu., and
cell volume V calculated for CeFe.sub.8M.sub.4 with M one of 26
elements other than Fe populating the 8i, 8j, or 8f sites in the
ThMn.sub.12 structure. The bold-data cells highlight the cases for
which .DELTA.H.sub.el is the most negative, indicating the greatest
stability with respect to the elemental constituents, for a given M
and lattice position.
The results suggest that CeFe.sub.12-xM.sub.x may be stabilized by
M=B, Al, Si, P, S, Sc, Ti, V, Co, Ni, Zn, Ga, Ge, Zr, Nb, Mo, Hf,
Ta, and W with Sc, Ti, V, Zr, Nb, Mo, Hf, Ta, W preferring the 8i
site and B, Al, Si, P, S, Co, Ni, Zn, Ga, Ge preferring the 8j
site. C, Na, Mg, Mn, Cu, and Sn are definitely not favorable in
view of the large, positive .DELTA.H.sub.el values. The small but
positive .DELTA.H.sub.el for CeFe.sub.8Cr.sub.4 (Cr filling the 8i
site) is consistent with the fact that RFe.sub.12-xCr.sub.x
compounds are known only for x.ltoreq.2.
The findings are in qualitative overall agreement with experiment
inasmuch as (i) CeFe.sub.12-xM.sub.x (M=Ti, V, Cr, Mo) compounds
have been reported previously and (ii) CeFe.sub.12-xSi.sub.x
(x=1.0, 1.5, 2.0) has been synthesized as part of this work. Table
I indicates that CeFe.sub.12-xM.sub.x (M=B, Al, P, S, Sc, Co, Ni,
Zn, Ga, Ge, Zr, Nb, Hf, Ta, and W) merit attempts to synthesize as
well. The Sc material, even if it were to form, is not interesting
from a technological perspective in view of the scarcity and
associated enormous cost of Sc. The M=Co, Ni, Zn, Ga, and Ge
compounds, on the other hand, may be particularly interesting since
their magnetic moments per formula unit in Table I are about twice
those of the M=Ti, V, Cr, and Mo compounds, which would afford
magnets with substantially greater energy products and likely
larger Curie temperatures. The relatively large cell volume of
CeFe.sub.8Zr.sub.4 may foreshadow the formation of trivalent Ce,
which would have a 4f magnetic moment that would contribute to the
overall magnetization and provide magnetocrystalline
anisotropy.
TABLE-US-00001 TABLE I Density functional theory calculation
results for CeFe.sub.8M.sub.4 compounds. M in 8i site M in 8j site
M in 8f site .DELTA.H.sub.el .mu. V .DELTA.H.sub.el .mu. V
.DELTA.H.sub.el .mu. V (kJ/mole .mu..sub.B/ (.ANG..sup.3/ (kJ/mole
.mu..sub.B/ (.ANG..sup.3/ (kJ- /mole (.mu..sub.B/ (.ANG..sup.3/
f.u.) f.u.) f.u.) f.u.) f.u.) f.u.) f.u.) f.u.) f.u.)
CeFe.sub.8B.sub.4 213 12.2 144.7 -151 10.5 140.7 -106 12.0 131.7
CeFe.sub.8C.sub.4 429 13.7 142.5 525 7.8 135.9 767 11.6 128.1
CeFe.sub.8Na.sub.4 637 18.3 212.4 945 17.4 231.8 929 19.3 240.6
CeFe.sub.8Mg.sub.4 145 16.3 196.0 293 16.3 197.3 417 16.6 199.5
CeFe.sub.8Al.sub.4 -268 14.1 178.3 -300 14.5 178.9 -192 14.6 177.9
CeFe.sub.8Si.sub.4 -324 12.6 167.5 -479 13.2 168.4 -409 11.8 161.6
CeFe.sub.8P.sub.4 -355 15.2 179.9 -555 12.4 165.2 -358 14.0 158.6
CeFe.sub.8S.sub.4 -169 22.1 190.1 -266 18.4 174.8 -11 17.6 173.6
CeFe.sub.8Sc.sub.4 -52 10.6 198.7 127 12.6 206.8 272 13.7 214.6
CeFe.sub.8Ti.sub.4 -253 7.9 179.0 -138 10.3 185.2 42 9.9 186.6
CeFe.sub.8V.sub.4 -149 8.2 168.3 -64 8.7 172.3 27 9.8 173.6
CeFe.sub.8Cr.sub.4 3 8.8 161.7 91 6.0 165.8 109 12.7 166.2
CeFe.sub.8Mn.sub.4 14 4.4 161.2 112 18.9 162.2 67 16.6 162.4
CeFe.sub.8Co.sub.4 -1 22.8 165.67 -63 23.1 165.72 -58 24.6 166.9
CeFe.sub.8Ni.sub.4 -28 18.3 165.46 -103 20.0 165.46 -76 21.8 167.3
CeFe.sub.8Cu.sub.4 103 16.2 169.9 76 16.7 169.4 145 18.5 171.2
CeFe.sub.8Zn.sub.4 5 15.9 178.7 -35 15.9 177.7 49 16.8 177.6
CeFe.sub.8Ga.sub.4 -185 15.4 180.9 -240 16.3 181.9 -123 15.8 179.3
CeFe.sub.8Ge.sub.4 -148 15.7 181.0 -268 15.4 181.9 -92 15.9 15.9
CeFe.sub.8Zr.sub.4 -78 10.6 202.8 98 11.7 213.0 271 11.3 219.1
CeFe.sub.8Nb.sub.4 -71 9.7 187.2 84 10.6 195.0 290 12.2 202.0
CeFe.sub.8Mo.sub.4 -13 9.1 178.0 168 8.7 183.0 255 14.9 191.7
CeFe.sub.8Sn.sub.4 37 17.9 210.8 31 17.6 213.5 251 18.3 218.1
CeFe.sub.8Hf.sub.4 -150 9.9 198.9 3 11.6 208.3 194 11.0 212.5
CeFe.sub.8Ta.sub.4 -148 8.9 187.4 3 10.4 193.7 220 10.6 199.9
CeFe.sub.8W.sub.4 -17 8.8 178.7 153 8.3 183.3 268 13.9 192.7
Alloys of CeFe.sub.11Si, CeFe.sub.10.5Si.sub.1.5, and
CeFe.sub.10Si.sub.2 were prepared by combining stoichiometric
quantities of elemental Ce, Fe, and Si. Ingots were prepared by
induction melting the elements under argon inert gas at
1420-1450.degree. C., holding the molten alloy at that temperature
for 3-5 minutes to ensure complete homogenization by induction
stirring. Pieces of the resulting homogenized ingot were placed in
a quartz ampule having a 0.65.+-.0.01 mm diameter orifice in the
bottom, remelted by induction heating to 1420-1450.degree. C., and
melt-spun by applying a 2.5-3.5 psi overpressure to eject the
molten alloy onto the circumference of a rapidly rotating
chromium-plated copper wheel (diameter D=25.4 cm). The surface
speed, v.sub.s, of the wheel was varied between 5 and 40 m/s to
alter the quench conditions. The resulting ribbon materials were
collected, ball milled into powder, and their properties examined
by X-ray diffraction (XRD) to determine crystal structure and phase
composition. Table II summarizes the compositions, wheel speeds,
and selected results.
TABLE-US-00002 TABLE II Summary of CeFe.sub.12-xSi.sub.x materials
Lattice Magnetic constants* moment Nominal Wheel speed v.sub.s a c
4.pi.M.sub.s T.sub.c composition (m/s) (.ANG.) (.ANG.) (Tesla)*
(.degree. C.)* CeFe.sub.11Si 5, 10, 15, 20, 25, 30 8.410 4.889 1.27
264 CeFe.sub.10.5Si.sub.1.5 5, 10, 15, 20, 25, 30, 8.405 4.841 1.20
293 35, 40 CeFe.sub.10Si.sub.2 5, 7.5, 10, 12.5, 15, 8.420 4.802
1.04 305 20, 25, 30, 35 *Values for ribbons melt-spun at 15 m/s
Rietveld analysis was applied to the XRD patterns from
CeFe.sub.11Si, CeFe.sub.10.5Si.sub.1.5, and CeFe.sub.10Si.sub.2
ribbons melt-spun at various wheel speeds. An example is shown in
FIG. 1 for CeFe.sub.10Si.sub.2 ribbons melt-spun at 15 m/s. The
Rietveld fit demonstrates that the major phase (more than 78 wt %
of the sample) has the ThMn.sub.12-type tetragonal crystal
structure, with the balance being Fe.sub.0.95Si.sub.0.05 and
Ce.sub.2Fe.sub.14Si.sub.3 (hexagonal Ce.sub.2Fe.sub.17 with partial
substitution of Si for Fe). Similar good fits were obtained for
other samples. FIG. 2 exhibits the phase fraction in weight
percentage for CeFe.sub.12-xSi.sub.x alloys melt spun at 5 m/s, 15
m/s, and 30 m/s respectively. For a fixed wheel speed v.sub.s, the
fraction of CeFe.sub.12-xSi.sub.x phase increases with increasing
x. For a fixed composition, a higher wheel speed favors the
formation of CeFe.sub.12-xSi.sub.x phase. FIG. 3 shows the lattice
constants a and c of the tetragonal crystal structure as a function
of Si content x in CeFe.sub.12-xSi.sub.x. The a axis is almost
independent of the Si content, while the c axis contracts linearly
with increasing Si content. FIG. 4 shows the crystallite size as a
function of wheel speed from the Rietveld full profile fitting; as
expected for rapidly quenched materials, the grain size is less
than 70 nm and decreases with increasing wheel speed (increasing
quench rate).
Curie temperatures T.sub.c were measured for each
CeFe.sub.12-xSi.sub.x alloy melt spun at 15 m/s, and the results
are given in Table II. Values of T.sub.c were obtained by
monitoring the temperature dependence of the magnetic force in a
small applied magnetic field using a Perkin-Elmer System 7
thermogravimetric analyzer (TGA). The Curie temperature is taken as
the point where the contribution to the magnetic force (i.e., the
magnetization) due to CeFe.sub.12-xSi.sub.x vanishes. The Curie
temperatures are the highest observed in Ce--Fe-based compounds to
date. Notably, T.sub.c increases with Si content even though the Fe
content of the Ce(Fe.sub.12-xM.sub.x) compound is reduced.
Nitriding of selected Ce(Fe.sub.12-xM.sub.x) ribbons with pure
nitrogen gas was performed in a Hiden Isochema Intelligent
Gravimetric Analyzer (IGA). The typical nitriding profile is set as
the following: temperature (T) 450-500.degree. C., time (t) 1-48
hours, and pressure (P) 20 bar of nitrogen gas. The powders were
sieved to 25-45 .mu.m sized particles prior to nitriding. The
nitrogen uptake was calculated from the change in sample weight at
approximately 1 bar and room temperature (20.degree. C.), before
and after nitrogenation, in order to eliminate the confounding
effect of buoyant forces at elevated pressure and temperature.
Typically Ce(Fe.sub.12-xM.sub.x) compounds can absorb one to three
nitrogen atoms per formula unit after being fully saturated by the
nitrogenation process.
XRD examinations of the nitrides show that the ThMn.sub.12
tetragonal crystal structure is retained, and that insertion of N
atoms into the lattice results in an overall increase in the unit
cell volume. Accompanying the lattice and volume expansions (shown
in FIG. 5), T.sub.c increases substantially relative to the
material before nitriding. For example, nitriding
CeFe.sub.10Si.sub.2 to CeFe.sub.10Si.sub.2N.sub.1.29 using 20 bar
of nitrogen gas at 450.degree. C. for 16 hours increases T.sub.c
from 305.degree. C. to 426.degree. C. The latter value is
noteworthy in that it is substantially larger than
T.sub.c=312.degree. C. of Nd.sub.2Fe.sub.14B, and thus is a very
promising material for further development as a permanent magnet.
The higher T.sub.c value results in a smaller change in properties
between room temperature and motor operating temperatures.
Previous literature reports on relevant RFe.sub.12-xM.sub.x suggest
that due to the atomic size difference, Ti and Si preferentially
occupy different sites in the lattice. The DFT calculations
performed on CeFe.sub.8Ti.sub.4 and CeFe.sub.8Si.sub.4 indicate
that Ti preferentially occupies the 8i site in the 1-12 lattice,
while the Si preferentially occupies the 8j site. The preferential
substitution of Ti and Si at different sites suggests that a series
of hypothetical quaternary compounds of the form
CeFe.sub.10+xSi.sub.2-2xTi.sub.x could result in lattice distortion
different from a single element substitution scheme, which offers a
new variable to tune the magnetic properties. The quaternary
CeFe.sub.10+xSi.sub.2-2xTi.sub.x could be perceived as a solid
solution of ternary CeFe.sub.10Si.sub.2 and CeFe.sub.11Ti.
Alloys of CeFe.sub.10Si.sub.2, CeFe.sub.10.25Si.sub.1.5Ti.sub.0.25,
CeFe.sub.10.5Si.sub.1Ti.sub.0.5,
CeFe.sub.10.75Si.sub.0.5Ti.sub.0.75, and Ce.sub.1.1Fe.sub.11Ti were
prepared by combining stoichiometric quantities of elemental Ce,
Fe, Si, and Ti. Ingots were prepared by induction melting the
elements under argon inert gas at 1375-1450.degree. C., holding the
molten alloy at that temperature for 3-5 minutes to insure complete
homogenization by induction stirring. Pieces of the resulting
homogenized ingot were placed in a quartz ampoule having a
0.65.+-.0.01 mm diameter orifice in the bottom, re-melted by
induction heating to 1380-1450.degree. C., and melt spun by
applying a 2.5-3.5 psi overpressure to eject the molten alloy onto
the circumference of a rapidly rotating chromium-plated copper
wheel (D=25.4 cm). The surface speed, v.sub.s, of the wheel was
varied between and 10 and 45 m/s to alter the quench conditions.
The resulting ribbon materials were collected, ball milled into
powder, and their properties examined by X-ray diffraction (XRD) to
determine crystal structure and phase composition. FIG. 6 displays
the x-ray diffraction patterns for CeFe.sub.10+xSi.sub.2-2xTi.sub.x
for x=0 (a), x=0.25 (b), x=0.5 (c), x=0.75 (d), and x=1 (e); where
x=0 and x=1 represent the ternary compounds CeFe.sub.10Si.sub.2,
and CeFe.sub.11Ti respectively. Note that the CeFe.sub.11Ti ingot
in this example was prepared with ten atomic percent excess cerium
content (i.e., Ce.sub.1.1Fe.sub.11Ti). It was found that the extra
cerium was beneficial in promoting the formation of the 1:12 phase
and in the retention of the 1:12 phase when they were nitrided. The
as-spun samples consisted of a primary ThMn.sub.12-type phase of
the respective ternary or quaternary compound with a minor Fe-based
impurity phase (identified as .alpha.-Fe in the figure). FIG. 7
displays the lattice constants (a) and (c) of the respective
ternary and quaternary compounds as functions of x.
Nitriding of selected CeFe.sub.10+xSi.sub.2-2xTi.sub.x ribbons was
performed in a Hiden Isochema Intelligent Gravimetric Analyzer
(IGA). The typical nitriding profile is set as the following:
temperature (T) 450.degree. C., time (t) 1-16 hours, and pressure
(P) 20 bar. The powders were sieved to smaller than 45 .mu.m sized
particles prior to nitriding. The nitrogen uptake was calculated
from the change in sample weight at approximately 1 bar and room
temperature (20.degree. C.) before and after nitrogenation, in
order to eliminate the confounding effect of buoyant forces at
elevated pressure and temperature. CeFe.sub.10Si.sub.2 exhibits the
highest T.sub.c=305.degree. C. and CeFe.sub.11Ti has the lowest
T.sub.c=215.degree. C.; the latter is in good agreement with the
value of T.sub.c=233.degree. C. previously reported in the
literature for CeFe.sub.11Ti. The T.sub.c for the quaternary
nitrides decreases monotonically with x. Curie temperatures are
greatly increased after nitrogenation, with the smallest
.DELTA.T.sub.c=121.degree. C. from CeFe.sub.10Si.sub.2 and the
largest .DELTA.T.sub.c=215.degree. C. from CeFe.sub.11Ti.
Quaternary compounds of the form CeFe.sub.10+xSi.sub.2-2xTi.sub.x
with x=0.25, 0.5, and 0.75 exhibit a Curie temperature enhancement
exceeding 150.degree. C., a larger enhancement compared to ternary
CeFe.sub.10Si.sub.2. Magnetic moment has also been increased in the
nitrides with the smallest increase of 12.8% in
CeFe.sub.10.25Si.sub.1.5Ti.sub.0.25 and the largest increase of
20.6% in CeFe.sub.10.75Si.sub.0.5Ti.sub.0.75. FIG. 8 displays the
Curie temperature of the CeFe.sub.10+xSi.sub.2-2xTi.sub.x compounds
and their nitrides.
Table III summarizes the lattice constants, magnetic moment
4.pi.M.sub.s, and Curie temperature for quaternary
CeFe.sub.10+xSi.sub.2-2xTi.sub.x and their nitrides. For the
nitrides, the rightmost column also gives the number y of N atoms
per CeFe.sub.10+xSi.sub.2-2xTi.sub.xN.sub.y formula unit as
determined from measured nitrogen weight gain during nitriding.
CeFe.sub.10.25Si.sub.1.5Ti.sub.0.25 and CeFe.sub.10.5SiTi.sub.0.5
were melt spun at wheel speed v.sub.s=15 m/s while
CeFe.sub.10.75Si.sub.0.5Ti.sub.0.75 was melt spun at v.sub.s=10
m/s. Except for CeFe.sub.11Ti, the nitrides listed in the table
have been nitrided at nitrogen pressure of 20 bar at 450.degree. C.
for 16 hours. As stated above, the CeFe.sub.11Ti starting material
listed in Table III was initially formed using 10 at % excess Ce in
the starting composition in order to promote formation of the
ThMn.sub.12 phase in both the as-formed melt-spun products and the
nitrided products. For CeFe.sub.11Ti the nitriding was completed at
a reduced pressure and temperature of 10 bar at 410.degree. C. for
18 hours.
TABLE-US-00003 TABLE III Lattice Magnetic constants moment Nominal
a c 4.pi.M.sub.s T.sub.c N atoms y composition (.ANG.) (.ANG.)
(Tesla) (.degree. C.) per f.u. CeFe.sub.10Si.sub.2 8.411 4.757 1.04
305 CeFe.sub.10.25Si.sub.1.5Ti.sub.0.25 8.434 4.766 1.09 278
CeFe.sub.10.5SiTi.sub.0.5 8.442 4.780 1.08 245
CeFe.sub.10.75Si.sub.0.5Ti.sub.0.75 8.454 4.815 1.02 222
CeFe.sub.11Ti 8.481 4.801 0.90 215 CeFe.sub.10Si.sub.2N.sub.y 8.490
4.790 1.16 426 1.29 CeFe.sub.10.25Si.sub.1.5Ti.sub.0.25N.sub.y
8.519 4.821 1.23 438 1.34 CeFe.sub.10.5SiTi.sub.0.5N.sub.y 8.545
4.880 1.27 406 1.87 CeFe.sub.10.75Si.sub.0.5Ti.sub.0.75N.sub.y
8.570 5.008 1.23 375 2.72 CeFe.sub.11TiN.sub.y 8.590 4.898 1.21 430
2.40
Thus, we have described a new family of permanent magnet materials
that contain a major weight proportion of one or more compounds of
CeFe.sub.12-xM.sub.x, having the ThMn.sub.12 crystal structure
(space group I4/mmm, #139) and with M being one or more of the
elements B, Al, Si, P, S, Sc, Co, Ni, Zn, Ga, Ge, Zr, Nb, Hf, Ta,
and W. Preferably, x is in the range of one to four. In addition,
one or more of Ti, V, Cr, and Mo may be combined with, or
substituted for, up to about ninety atomic percent of an M element
in the CeFe.sub.12-xM.sub.x compound.
The material may be prepared from a melt of the constituent
elements by rapid solidification to form with a major portion of
the CeFe.sub.12-xM.sub.x compound. The material may be prepared in
the form of a powder or other form for shaping and consolidating
into a permanent magnet body for an electric motor or other desired
product application. And the permanent magnet material may be
nitrided to increase its Curie temperature and its permanent magnet
properties.
Practices of the invention have been illustrated by specific
examples which are not intended to limit the scope of the
invention.
* * * * *